Here we report atomic structure calculations and experimental observations of the two-photon
6s21S0→6s23s1S0 transition in Yb. The unique level structure of Yb places the
6s6p1P1 state's energy at
≈49.7% of the ionization energy, which facilitates two-photon Doppler-free excitation of the
6s23s1S0 Rydberg state from the
6s21S0 ground state at a relatively low optical intensity. This
J=0→J=0 transition is immune to first-order Zeeman and electric quadrupole shifts, has reduced sensitivity to higher-order Zeeman shifts, and is further predicted to have relatively low sensitivity to density shifts. Using configuration interaction theory, we compute relevant properties of the
6s23s1S0 Rydberg state for sensing, including the
C6 coefficient, dc polarizability, blackbody radiation (BBR) shift, and BBR depopulation rate. As a first experimental step, we demonstrate two-photon Doppler-free spectroscopy of the
6s21S0→6s23s1S0 transition. From our experimental spectra, we estimate the natural linewidth (lifetime) of the
6s23s1S0 state to be 90 kHz (1.8
μs). We believe this transition, or other
6s21S0→6sns1S0 transitions in Yb with
n≈23, may find use in a variety of sensing applications, potentially including a two-photon clock, electrometer, or BBR thermometer.